(Quinolinyl and quinoxalinyloxy)phenoxy alkenols and their use as post emergent herbicides

ABSTRACT

Compounds of the class comprising (quinolinyl and quinoxalinyloxy)phenoxy) alkenols, e.g., 4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol; and a method of preparation, comprising reacting an appropriately substituted quinoline or quinoxaline, e.g., 2,6-dichloroquinoline, with a phenolic substituted pentenol, e.g., 4-(4-hydroxyphenoxy)-2-penten-1-ol, in the presence of a base and organic solvent under an inert atmosphere with or without heat, and then recovering the product. 
     These compounds are useful as intermediates for preparing various known herbicidal compounds and are useful in their own right as post-emergent herbicides for controlling grassy weeds in the presence of corn plants.

BACKGROUND OF THE INVENTION

Highly active herbicidal compounds of the class constitutingaryloxyphenoxyalkanoic, and aryloxyphenoxyalkenoic acids and relatedcompounds have been described in the patent literature. These compoundshave been prepared by making derivatives of the acid function thereofand bearing various groups or substituents on, primarily, the arylstructure. Such compounds in which the aryloxy and O-alkanoic acidfunctions respectively are disposed in 1,4 relation on the phenyl group,are especially active against grassy, i.e., gramineous weeds whiledisplaying little or no herbicidal activity against broadleaf plantsand, often, only slight activity against cereal grains. However, thesecompounds as a group are generally injurious to corn, i.e., maize, andare of little use for controlling grassy weeds in corn crops.

SUMMARY OF THE INVENTION

The present invention relates to novel 4-((aryloxy)phenoxy)alkenolswhich are useful as intermediates for preparing highly active herbicidalcompounds, which compounds are particularly effective in selectivelycontrolling grassy weeds in the presence of corn plants. In addition,these compounds are active herbicides in their own right and are usefulin controlling grassy weeds and especially controlling grassy weeds inthe presence of many broadleaf crop plants.

The aryloxyphenoxyalkenols of the present invention correspond to theformula ##STR1## wherein

Y and Y¹ each independently represent --H or --F;

P represents methyl or ethyl;

T represents --CH₂ --CH₂)_(a) (CH═CH--_(b) and the cis (Z) or trans (E)stereoisomers thereof or --CH₂ --)CH₂)_(a) C.tbd.C--;

A represents .tbd.N or .tbd.CH;

a represents the integer 0, 1 or 2;

b represents the integer 1 or 2; and

X represents --Br, --Cl, --F or --CF₃.

The term "C₁ -C₄ alkyl" as employed in the present specification andclaims designates alkyl groups which can be straight or branched chaincontaining from 1 to 4 carbon atoms or cycloalkyl of 3 or 4 carbonatoms.

In the present invention, it is to be noted that all substituent groupsare sterically compatible with each other. The term "stericallycompatible" is employed to designate substituent groups which are notaffected by steric hindrance as this term is defined in "The CondensedChemical Dictionary", 7th edition, Reinhold Publishing Co., N.Y., page893 (1966) which definition is as follows:

"steric hindrance. A characteristic of molecular structure in which themolecules have a spatial arrangement of their atoms such that a givenreaction with another molecule is prevented or retarded in rate."

Sterically compatible may be further defined as reacting compoundshaving substituents whose physical bulk does not require confinementwithin volumes insufficient for the exercise of their normal behavior asdiscussed in "Organic Chemistry" of D. J. Cram and G. Hammond, 2ndedition, McGraw-Hill Book Company, N.Y., page 215 (1964).

The compounds of the present invention contain the optically activecenter ##STR2## and can exist in optically active stereoisomeric formssuch as the R and S enantiomeric forms. The use of the various mixturesand racemates of the above isomers are within the scope of the presentinvention. Additionally, the R enantiomer of such compounds have beenfound to be more active biologically than the S enantiomer and may beused whenever the greater activity justifies the extra expenses for theuse of this isomer.

In addition, the compounds of the present invention can contain isomersof the geometric isomer class which result from a carbon-carbon doublebond. The resulting isomers are called cis (Z) and trans (E) isomers.

A general discussion of the isomer activity difference phenomenon can befound in A. Albert, Selective Toxicity, 4th edition, Met Luen & Co.,Ltd., London, 1968, pp. 387-390 and more particular discussions in A.Fredga and B. Åberg, "Stereoisomerism in plant growth regulators of theauxin type", Ann. Rev. Plant Physiology 16:53-72, 1965, and in E. J.Lien, J. F. R. DeMiranda and E. J. Airens, "Quantitativestructure-activity correlation of optical isomers", MolecularPharmacology 12:598-604, 1976.

The compounds of the present invention are generally oils or low meltingcrystalline solids at ambient temperatures which are soluble in manyorganic solvents.

Representative compounds of the present invention are set forth below inTable 1.

                                      TABLE 1                                     __________________________________________________________________________     ##STR3##                                                                     A    X    Y   Y.sup.1                                                                           P    T                                                      __________________________________________________________________________    CH   F    H   H   C.sub.2 H.sub.5                                                                    (CHCH) .sub.2                                          N    Cl   H   H   CH.sub.3                                                                           CHCH                                                   CH   Br   H   H   CH.sub.3                                                                           CHCH                                                   N    F    H   H   CH.sub.3                                                                           CHCH                                                   N    Cl   H   H   C.sub.2 H.sub.5                                                                    CHCH                                                   N    CF.sub.3                                                                           H   H   CH.sub.3                                                                           CHCH                                                   CH   Cl   H   H   CH.sub.3                                                                           (CHCH) .sub.2                                          N    Cl   H   H   CH.sub.3                                                                           (CHCH) .sub.2                                          N    F    H   H   CH.sub.3                                                                           (CHCH) .sub.2                                          CH   CF.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                    (CHCH) .sub.2                                          N    CF.sub.3                                                                           H   H   CH.sub.3                                                                           (CHCH) .sub. 2                                         N    Cl   F   H   CH.sub.3                                                                           CHCH                                                   N    F    H   F   CH.sub.3                                                                           CHCH                                                   N    Cl   F   H   C.sub.2 H.sub.5                                                                    CHCH                                                   CH   Cl   F   F   C.sub.2 H.sub.5                                                                    (CH.sub.2 CH.sub.2 ) .sub.2(CHCH) .sub.2               N    Cl   H   H   C.sub.2 H.sub.5                                                                    (CHCH) .sub.2                                          N    CF.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                    CHCH                                                   CH   Cl   H    H  CH.sub.3                                                                           CHCH                                                   CH   Cl   F   H   C.sub.2 H.sub.5                                                                    CHCH                                                   CH   F    F   F   CH.sub.3                                                                           CHCH                                                   CH   Cl   F   F   CH.sub.3                                                                           CHCH                                                   __________________________________________________________________________

The 4-((aryloxy)phenoxy)alkenols of the present invention correspondingto the formula ##STR4## can be prepared by the reaction of substantiallyequimolar amounts of an appropriate compound corresponding to theformula ##STR5## where X and A are as hereinbefore defined and X¹represents --Br, --Cl, --F or --SO₂ R¹ and R¹ is C₁ -C₄ alkyl with anappropriate alkenol derivative corresponding to the formula ##STR6##wherein Y, Y¹, P and T are as hereinbefore defined. In carrying out thisreaction, the reactants and a strong base such as an anhydrous alkalimetal hydride, alkoxide, hydroxide or carbonate are mixed together in adipolar, aprotic solvent such as, for example, dimethylformamide (DMF),acetone, methyl ethyl ketone, acetonitrile, diomethylsulfoxide (DMOS),sulfolane, N-methylpyrrolidone or the like. The reaction isadvantageously carried out at elevated temperatures of from about 50° to120° C.

The specific reaction times employed in the hereinabove and hereinafterset forth preparative procedures vary considerably and are dependentupon factors such as the solvent, base, catalyst, if employed, reactiontemperature and the reactivity of the specific reactants employed. Thereactions are for the most part complete in a period of from about 30minutes to about 12 hours or more.

This procedure is also the preferred procedure to use when Y and Y¹ areboth fluorine.

The compound of Formula I wherein Y and Y¹ are both hydrogen and A is.tbd.CH can also be prepared by the reaction of an appropriatearyloxyphenol corresponding to the formula ##STR7## with an appropriatea-haloalkenoic acid ester corresponding to the formula ##STR8## whereinP, R¹ and T are as hereinbefore defined, and Hal is --Cl or --Bremploying the same reaction conditions as set forth hereinabove for thereaction between the reactants of Formulae II and III.

The ester product corresponding to the formula ##STR9## is reduced tothe corresponding 4-((aryloxy)phenoxy)alkenol of Formula I. Thereduction of the ester of Formula VI is conveniently carried out byreaction of said ester with a reducing agent such as, for example,diisobutylaluminum hydride (DIBAL-H) or lithium aluminum hydride (LAH)in an inert solvent. The solvent and reaction temperature employeddepend primarily upon the specific reducing agent. When DIBAL-H isemployed, the reaction temperature is within the range of about -78° toabout +25° C. and the solvents include toluene, ether or cyclohexane.When LAH is employed, the reaction is conducted by refluxing the esterin a solvent such as ether or tetrahydrofuran.

The hydroxyphenoxy alkenols corresponding to the formula ##STR10## areprepared by a variety of procedures. Those compounds wherein Y and Y¹are both hydrogen, are for the most part known compounds and are taughtin U.S. Pat. Nos. 4,263,040 and 4,360,375; and Japanese Kokai J56034-647and J56034-648.

Those compounds of Formula III wherein Y and/or Y¹ are fluorine can beprepared in a multistep procedure as follows: ##STR11## No attempt hasbeen made to present a balanced equation in the above reaction sequence.

The above reaction steps can be carried out as follows:

Step A

The appropriate fluorophenol of Formula VII in a solvent such as, forexample, methylene chloride is reacted for from about 1 to about 3 hourswith 90 percent nitric acid at a temperature of from about -15° C. toabout 5° C. At the end of this period, the desired 2-fluoro- or2,6-difluoro-4-nitrophenol product of Formula VIII is recoveredemploying conventional procedures.

Step B

The thus formed 2-fluoro- or 2,6-difluoro-4-nitrophenol of Formula VIIIis reacted with an appropriate α-alkenoic acid ester, corresponding toFormula V. In carrying out this reaction, the compound of Formula V, thephenol compound of Formula VIII and a base metallic base such as sodiumor potassium carbonate, or an organic base such as triethylamine aremixed together in the presence of a solvent such as dimethylsulfoxide(DMSO), dimethylformamide, tetrahydrofuran, acetonitrile,hexamethylphosphoramide or N-methylpyrrolidone and heated to atemperature between about 40° C. to about 220° C. The desiredfluorinated 4-nitrophenoxy alkenoic acid ester corresponding to FormulaIX is recovered employing conventional procedures.

Step C

The thus formed fluorinated 4-nitrophenoxyalkenoic acid estercorresponding to Formula IX is selectively reduced to the correspondingamino (aniline) compound corresponding to Formula X. This reduction canbe conveniently carried out employing conventional stannous chloridereduction procedure. The product is recovered employing conventionalrecovery procedures.

Step D

The thus formed aniline compound corresponding to Formula X is treatedwith an aqueous solution of concentrated HCl at a temperature of fromabout 0°-10° C. and this solution is then reacted with an aqueoussolution of an alkali metal nitrite. This mixture is thereafter reactedwith an aqueous solution of fluoroboric acid to form the desiredcorresponding diazonium tetrafluoroborate compound corresponding toFormula XI. The product is separated employing conventional procedure.

Step E

The thus formed compound corresponding to Formula XI is treated underreflux conditions with a mixture of an alkali metal trifluoroacetate intrifluoroacetic acid to obtain the desired product compoundcorresponding to Formula XII.

The hydroxyphenoxy alkenoic acid ester corresponding to Formula XII canthen be reduced to the corresponding hydroxyphenoxyalkenol of FormulaIII employing the procedure set forth hereinabove employed for reducingthe compound of Formula VI to the compound of Formula I.

The heterocyclic halides employed as starting materials and whichcorrespond to the formula ##STR12## wherein A, X and X¹ are ashereinbefore defined, are all known and/or commercially producedcompounds and for the most part are taught in the above-listedapplications and/or patents which teach preparing compounds of FormulaIV.

The α-haloalkenoic acid esters employed as a starting material andcorresponding to the formula ##STR13## wherein Hal, P, R¹ and T are ashereinbefore defined are all known compounds and such compounds aretaught in European Patent Application No. 42750.

The following examples illustrate the present invention and the mannerby which it can be practiced but, as such, are not to be construed aslimitations upon the overall scope thereof.

The compounds obtained in the following examples were characterized byinfrared and/or nuclear magnetic resonance spectrometry.

EXAMPLE 1 E isomer of 4-(4-hydroxyphenoxy)-2-penten-1-ol ##STR14##

An oven-dried flask was equipped with a nitrogen inlet, a stirrer, athermometer and a septum stoppered dropping funnel and was flushed withnitrogen. The flask was charged with a solution of 26.6 grams (g) (120millimole (mmol)) of methyl (E)-4-(4-hydroxyphenoxy)-2-pentenoate in 150milliliters (ml) of toluene. The solution was cooled to -78° C., and thedropping funnel was charged with 250 ml (375 mmol) of 25 percent (%)solution of diisobutylaluminum hydride (DIBAL) in toluene. The DIBALsolution was then added at -78° C. dropwise to the reaction mixture overa 1.5 hour period, and the reaction was stirred at -78° C. for anadditional 0.5 hour. The reaction was quenched by cautious, dropwiseaddition of 250 ml of a stock solution prepared from 6 parts of water,25 parts of acetic acid and 75 parts of ether while maintaining thetemperature below -50° C. The resulting mixture was allowed to warm toroom temperature and filtered, and the solid was washed with ether. Thefiltrates were combined and reserved while the solid was partitionedbetween water and ether.

This mixture was made acidic with aqueous HCl, and the ether layerseparated and combined with the reserved filtrates. The combined organicsolution was then washed to neutrality with saturated aqueous sodiumbicarbonate, dried over MgSO₄ and evaporated to dryness. The oilyresidue was then purified by preparative scale liquid chromatography(HPLC) eluting with 3:2 hexane: acetone removal of solvent and throughdrying left 19.3 g (83%) of the desired alcohol as a tan oil. (CompoundA).

    ______________________________________                                        Elemental Analysis:                                                                              % C  % H                                                   ______________________________________                                        Calculated for C.sub.11 H.sub.14 O.sub.3 :                                                         68.02  7.26                                              Found:               67.24  7.26                                              ______________________________________                                    

EXAMPLE 2 E-isomer of4-(4-((6-chloro2-quinolinyl)oxy)phenoxy)-2-penten-1-ol ##STR15##

A mixture of 3.06 g (15.4 mmol) of 2,6-dichloroquinoline, 3.00 g (15.4mmol) of (E)-4-(4-hydroxyphenoxy)-2-penten-1-ol, 2.34 g (16.9 mmol) ofpowdered, anhydrous potassium carbonate and 50 ml of drydimethylsulfoxide was warmed at 100°-110° C. for a period of 6 hours.The mixture was cooled to room temperature, poured over ice andextracted three times with ether. The combined ether layers were washedonce with 1 percent aqueous sodium hydroxide then with water, dried overMgSO₄ and evaporated to dryness. The residue was purified by preparativescale HPLC, eluting with 72:28 hexane:acetone, and then thoroughly driedto leave 2.9 g of the desired pentenol as a brown gum. (Compound B).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.20 H.sub.18 ClNO.sub.3 :                                                    67.51    5.10   3.94                                       Found:             67.11    5.24   3.78                                       ______________________________________                                    

EXAMPLE 3 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol ##STR16##

A mixture of 1.99 g (10 mmol) of 2,6-dichloroquinoxaline, 2.13 g (11mmol) of 4-(4-hydroxyphenoxy)-2-penten-1-ol, 1.73 g (12.5 mmol) ofpowdered, anhydrous potassium carbonate and 50 ml of dry acetonitrilewas warmed at reflux under nitrogen for a period of 3 hours. The mixturewas cooled to room temperature, and the solid filtered off and washedwell with ether. The filtrates were combined and evaporated to dryness,and the residue partitioned between ether and 2 percent aqueous sodiumhydroxide. The aqueous layer was separated and extracted again withether. The combined organic layers were washed with water, dried overMgSO₄ and evaporated to dryness. The residual solid was purified bypreparative scale HPLC, eluting with 7:3 hexane:ethyl acetate, to give asolid which was recrystallized from toluene. This gave 2.60 g (73%) ofthe desired pentenol as pale yellow crystals, having a melting point(m.p.) of 124°-126° C. (Compound C).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.19 H.sub.17 ClN.sub.2 O.sub.3 :                                             63.95    4.80   7.85                                       Found:             63.73    4.75   7.81                                       ______________________________________                                    

EXAMPLE 4

4-(4-((6-Bromo-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol ##STR17##

A mixture of 3.76 g (15.4 mmol) of 6-bromo-2-chloroquinoxaline, 3.00 g(15.4 mmol) of 4-(4-hydroxy- phenoxy)-2-penten-1-ol, 2.34 g (16.9 mmol)of powdered, anhydrous potassium carbonate and 50 ml of drydimethylsulfoxide was stirred at room temperature for a period of 24hours. The mixture was poured over ice and extracted three times withether. The combined ether layers were washed with 1 percent aqueoussodium hydroxide, then with water, dried over MgSO₄ and evaporated todryness. The residue was recrystallized from toluene to give 2.50 g ofthe desired pentenol as a yellow solid. (Compound D).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.19 H.sub.17 BrN.sub.2 O.sub.3 :                                             56.87    4.27   6.98                                       Found:             57.06    4.33   6.79                                       ______________________________________                                    

EXAMPLE 5 4-(4-((6-Fluoro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol##STR18##

A mixture of 3.63 g (20 mmol) of 2-chloro-6fluoroquinoxaline, 4.27 g (22mmol) of 4-(4-hydroxy-phenoxy)-2-penten-1-ol, 3.31 g (24 mmol) ofpowdered, anhydrous potassium carbonate and 30 ml of drydimethylsulfoxide was warmed at 120° C. for a period of 5 hours. Themixture was cooled to room temperature, poured over dilute aqueous HCl,and the resulting aqueous mixture was extracted two times with ether.The combined ether layers were washed twice with 5 percent aqueoussodium hydroxide, then with water, dried over MgSO₄ and evaporated todryness. The residue was purified by preparative scale HPLC, elutingwith 4:1:hexane:acetone, and then thoroughly dried to give 2.44 g of thedesired pentenol as a tan gum. (Compound E).

    ______________________________________                                        Elemental Analysis:                                                                           % C     % H    % N                                            ______________________________________                                        Calculated for C.sub.20 H.sub.18 FNO.sub.3 :                                                    70.78     5.35   4.13                                       Found:            70.09     5.23   4.16                                       ______________________________________                                    

EXAMPLE 6 4-(4-((6-Fluoro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol##STR19##

A mixture of 1.28 g (7 mmol) of 2-chloro-6fluoroquinoxaline, 1.16 g (8.4mmol) of anhydrous, powdered potassium carbonate, 1.55 g (8 mmol) of4-(4-hydroxyphenoxy)-2-penten-1-ol and 20 ml of DMSO was warmed, undernitrogen, at 110° C. for a period of 2 hours. The mixture was cooled toroom temperature, poured into dilute, aqueous HCl and extracted with twoportions of ether. The combined organic layers were washed twice with 1percent aqueous NaOH and with water, dried over MgSO₄ and evaporated todryness. The residue was purified by preparative scale HPLC, elutingwith 3:1 hexane:acetone. After removal of solvent the resulting tancrystals were recrystallized from methylcyclohexane to give 1.05 g ofcrystals which were further purified by recrystallization from tolueneto leave nearly colorless crystals, m.p. 109-111° C. (Compound F)

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.19 H.sub.17 FN.sub.2 O.sub.3 :                                              67.05    5.04   8.23                                       Found:             66.04    5.07   8.01                                       ______________________________________                                    

As indicated hereinabove, the novel 4-((aryloxy)phenoxy)alkenols of thepresent invention are herbicides and are useful in controlling grassyweeds and especially controlling grassy weeds in the presence ofbroadleaf crop plants both pre- and postemergently.

The alkenols of the present invention are also useful as intermediatesin the preparation of herbicidally active derivatives. These so preparedderivatives correspond to the formula ##STR20## wherein Y and Y¹ eachindependently represent --H or --F;

P represents methyl or ethyl;

T represents --CH₂ --CH₂)_(a) CH═CH--_(b) and the cis (Z) or trans (E)stereoisomers thereof or --CH₂ --CH₂)_(a) C.tbd.C--;

A represents .tbd.N or .tbd.CH;

a represents the integer 0, 1 or 2;

b represents the integer 1 or 2;

X represents --Br, --Cl, --F, or --CF₃ ;

R² represents --OSO₂ R³, ##STR21## R³ represents C₁ -C₄ alkyl, C₂ -C₄alkenyl or NR⁴ R⁵ ;

R⁴ represents C₂ -C₄ alkenyl, C₁ -C₄ alkyl, --NR⁵ R⁶ or ##STR22##wherein R⁵ and R⁶ each independently represent --H or C₁ -C₄ alkyl;

D represents C₁ -C₄ alkyl, --Br, --Cl, --NO₂, --CF₃, --OCF₃, ##STR23##wherein R⁷ represents C₁ -C₄ alkyl and m represents an integer of from0-3, inclusive.

The above active derivative compounds have been found to be useful asherbicides for the postemergent kill and control of undesirablevegetation, for example, grassy or graminaceous weeds in the presence ofcorn plants.

The term "herbicide" is used herein to mean an active ingredient whichcontrols or adversely modifies the growth of plants because ofphytotoxic or other effects substantial enough to seriously retard thegrowth of the plant or further to damage the plant sufficiently to killthe plant.

The terms "growth controlling" or "herbicidally effective" amount areemployed to designate an amount of active ingredient which causes amodifying effect and includes deviations from natural development,killing, regulation, dessication, retardation, and the like.

The term "plants" means established vegetation.

The terms "control" or "controlling" as it relates to plant growth hasthe same meaning as employed hereinabove for the term "herbicide".

The derivative compounds wherein R² is ##STR24## or --OSO₂ R³ and R³ andR⁴ are other than --NHR⁶ can be prepared by the condensation of anappropriate 4-((aryloxy)phenoxy)alkenol corresponding to the formula##STR25## with an appropriate halide corresponding to the formula

    Hal--R.sup.8                                               (XIV)

wherein R⁸ is ##STR26## or --SO₂ R³ and R³, R⁴ is as further defineddirectly hereinabove and R⁵ is other than hydrogen in the presence of aninert solvent and a hydrogen halide absorber (acid scavenger) to obtainthe desired compound corresponding to the formula ##STR27## where inFormulae I, XIV and XV; A, X, Y, Y¹, P, R², T and Hal are as hereinabovedefined.

The reaction is generally carried out at a temperature in the range offrom about 0° to about 25° C.

While not normally necessary, a catalyst can be employed, if desired.Representative catalysts include, for example, 4-dimethylaminopyridineand 1,4-diazabicyclo-2,2,2-octane.

Representative inert solvents for this reaction include, for example,chlorinated hydrocarbons (for example, methylene chloride), ether,toluene, pyridine, hexane, acetonitrile and the like.

Representative hydrogen halide absorbers include tertiary amines, alkalimetal hydroxides and alkali metal carbonates. Alternatively, it has alsobeen found that the addition of a molar excess of the amine reactant canfunction as the hydrogen halide absorber. Additionally, when pyridine isemployed as the solvent, it can also function as the hydrogen halideabsorber.

Additionally, when R² is ##STR28## and R⁴ is other than --NR⁵ R⁶, anappropriate anhydride corresponding to the formula ##STR29## wherein R⁴is as hereinbefore defined can be reacted with the alkenol correspondingto Formula I employing the same procedure and conditions as set forthhereinabove for the reaction between the reactants of Formulae I andXIV.

Further, when R² is ##STR30## and R⁴ is C₂ -C₄ alkenyl or C₁ -C₄ alkyl,an appropriate ester corresponding to the formula ##STR31## wherein P isas hereinbefore defined and R⁹ is C₂ -C₄ alkenyl or C₁ -C₄ alkyl isreacted with the alkenol corresponding to Formula I employing the sameprocedure and conditions as set forth hereinabove for the reactionbetween the reactants of Formulae I and XIV.

The derivative compounds wherein R² is ##STR32## and R are --NHR⁶ can beprepared by the condensation of an appropriate alkenol of Formula I withan appropriate isocyanate or isothiocyanate corresponding to the formula

    R.sup.6 NC═O/S                                         (XVIII)

wherein R⁶ is as hereinbefore defined. The reaction is generally carriedout in the presence of an inert solvent such as methylene chloride ortoluene at ambient temperatures, though the use of higher temperaturescould be necessary depending on the S/O═CNR⁶ reactant to effectcondensation. A catalytic amount of a base such as, for example,triethylamine, is sometimes beneficial. The isocyanate reactants are allknown compounds of commerce.

The derivative compounds which correspond to the formula ##STR33##wherein P, A, X, Y, Y¹, T and m are as hereinbefore set ##STR34## forthand D¹ is and R⁷ is as hereinbefore defined, can be prepared by thereaction, at ambient temperature, of an appropriate4-((aryloxy)phenoxy)alkenol corresponding to the formula ##STR35##wherein P, A, X, Y, Y¹ and T are as hereinbefore set forth with anappropriate substituted benzoic acid corresponding to the formula##STR36## wherein D¹ and m are as hereinbefore set forth in the presenceof a solvent such as DMF, methylene chloride or ether and in thepresence of a catalyst such as 4-(dimethylamino)pyridine and an aid forforming esters at low temperatures. Representative of such agents arecarbodiimides such as dicyclohexylcarbodiimide.

The desired product can be separated from the reaction mixture of theabove preparative procedures employing conventional separatoryprocedures known to those skilled in the art including steps of solventextraction, filtration, water washing, column chromatography,neutralization, acidification, crystallization and distillation.

Since the hereinabove and hereinafter set forth compound preparationprocedures employ only standard chemistry practices, and it is knownthat slightly different reactants can require slightly differentreaction parameters from those for other reactants, it is to beunderstood that minor modifications to the reaction parameters set forthsuch as the use of an excess of one reactant, the use of a catalyst, theuse of high temperature and/or pressure equipment, high speed mixing andother such conventional changes are within the scope of this invention.

The following examples further illustrate the present invention and themanner by which it can be practiced.

EXAMPLE 7 E isomer of4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy-2-penten-1-ol, 1-methylethylsulfonate ##STR37##

A solution prepared from 1.07 g (3 mmol) of the pentenol obtained inExample 2, 0.40 g (4 mmol) of triethylamine, and 20 ml of methylenechloride was cooled at 0° C. under nitrogen and a solution of 0.50 g(3.5 mmol) of isopropylsulfonylchloride in 3 ml of methylene chloridewas added in one portion. The resulting solution was stirred at 0° C.for 30 minutes and then poured into a mixture of ether and about 1Naqueous HCl. The organic layer was separated, dried over MgSO₄ andevaporated to dryness. The residue was purified by preparative scaleHPLC, eluting with 3:1 hexane:ethyl acetate, and then dried in aKugelrohr apparatus at 50° C. and 0.1 mm Hg for 1 hour. This left 1.31 g(95%) of desired sulfonate product as a viscous oil. (Compound 1).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.23 H.sub.24 ClNO.sub.5 S:                                                   59.80    5.24   3.03                                       Found:             58.91    5.11   2.90                                       ______________________________________                                    

EXAMPLE 8 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)2-penten-1-ol, 1-methylethylsulfonate ##STR38##

A solution prepared from 1.78 g (5 mmol) of the pentenol obtained inExample 3 above, 0.61 g (6 mmol) of triethylamine and 25 ml of methylenechloride was cooled under N₂ at 0° C. while 0.78 g (5.5 mmol) ofisopropylsulfonylchloride was added in one portion. After stirring at 0°C. for 45 minutes, the mixture was poured into a mixture of ether andwater. The organic layer was separated, dried over MgSO₄ and evaporatedto dryness. The residual solid was taken up in boiling hexane, filteredwhile hot and allowed to cool to give pale yellow crystals. The crystalswere filtered and dried to give 1.65 g (71%) of the desired sulfonateproduct, m.p. 95°-96° C. (Compound 2).

    ______________________________________                                        Elemental Analysis:                                                                             % C    % H    % N                                           ______________________________________                                        Calculated for C.sub.22 H.sub.23 ClN.sub.2 O.sub.5 S:                                             57.07    5.01   6.05                                      Found:              56.78    4.92   5.96                                      ______________________________________                                    

By following the procedure of Examples 4 and 5 employing the appropriatestarting pentenols and sulfonyl or sulfamoyl halids, the followingcompounds in Table 2 are prepared.

                                      TABLE 2                                     __________________________________________________________________________     ##STR39##                                                                                              Molecular Formula and                               Compound       M.P. °C. or                                                                       Elemental Analysis                                  No.   R.sup.2  RI at (n.sub.D.sup.25)                                                                   % C % H % N                                         __________________________________________________________________________                              C.sub.22 H.sub.24 ClN.sub.3 O.sub.5 S               3     NHCH(CH.sub.3).sub.2                                                                   73-75  Calc:                                                                             55.28                                                                             5.06                                                                              8.79                                                              Found:                                                                            55.59                                                                             5.09                                                                              8.68                                                                  C.sub.20 H.sub.19 ClN.sub.2 O.sub.5 S               4     CH.sub.3 115-116                                                                              Calc:                                                                             55.23                                                                             4.40                                                                              6.44                                                              Found:                                                                            54.94                                                                             4.30                                                                              6.34                                                                  C.sub.21 H.sub.21 ClN.sub.2 O.sub.5 S               5     C.sub.2 H.sub.5                                                                        95-97  Calc:                                                                             56.18                                                                             4.72                                                                              6.24                                                              Found:                                                                            56.27                                                                             4.58                                                                              6.14                                                                  C.sub.22 H.sub.23 ClN.sub.2 O.sub.5 S               6     C.sub.3 H.sub.7                                                                        81-83  Calc:                                                                             57.07                                                                             5.01                                                                              6.05                                                              Found:                                                                            56.44                                                                             4.91                                                                              5.94                                                                  C.sub.23 H.sub.25 ClN.sub.2 O.sub.5 S               7     C.sub.4 H.sub.9                                                                        85-87  Calc:                                                                             57.91                                                                             5.28                                                                              5.87                                                              Found:                                                                            57.89                                                                             5.16                                                                              5.71                                        __________________________________________________________________________

EXAMPLE 9 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol, acetate##STR40##

To an ice-cooled nitrogen flushed solution of 1.78 g (5 mmol) of thepentenol obtained in Example 3 above in 10 ml of pyridine was added 0.61g (6 mmol) of acetic anhydride. The resulting solution was allowed towarm to room temperature and stirred under nitrogen overnight. Thesolution was then poured into a mixture of ether and water. The organiclayer was separated and washed three times with 2 percent aqueous HCland saturated aqueous NaHCO₃, dried over MgSO₄ and evaporated to leavean off-white solid. The solid was purified by filtration, usingmethylene chloride as the solvent, through a short plug of silica gel,and then, after removal of solvent, recrystallized frommethylcyclohexane. This gave colorless crystals which were filtered,washed with hexane and dried to give 1.27 g (64%) of the desired acetateas colorless crystals, m.p. 89°-90° C. (Compound 8).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.21 H.sub.19 ClN.sub.2 O.sub.4 :                                             63.24    4.80   7.03                                       Found:             62.49    4.70   6.89                                       ______________________________________                                    

EXAMPLE 10 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol, benzoate##STR41##

A nitrogen flushed solution of 1.78 g (5 mmol) of the pentenol obtainedin Example 3 in 20 ml of pyridine was cooled in an ice bath and 0.77 g(5.5 mmol) of benzoylchloride was slowly added. The resulting mixturewas stirred at 0° C. for 1 hour and then at ambient temperature for 2hours. The reaction mixture was then poured into a mixture of water andether. The organic layer was separated, washed twice with 1N aqueous HCland then with saturated aqueous NaHCO₃, dried over MgSO₄ and evaporatedto dryness. After standing at room temperature, the residue slowlycrystallized and the solid was recrystallized from methylcyclohexane togive, after filtering and drying, 1.90 g (82%) of the desired benzoateas colorless crystals melting at 79°-81° C. (Compound 9).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.26 H.sub.21 ClN.sub.2 O.sub.4 :                                             67.75    4.59   6.08                                       Found:             67.56    4.49   6.08                                       ______________________________________                                    

By substantially following the procedures of Example 6 employing theappropriate starting pentenols and acid halide in pyridine, thefollowing compounds in Table 3 are prepared.

                                      TABLE 3                                     __________________________________________________________________________     ##STR42##                                                                                                Molecular Formula and                             Compound         M.P. °C. or                                                                       Elemental Analysis                                No.   R.sup.2    RI at (n.sub.D.sup.25)                                                                   % C % H % N                                       __________________________________________________________________________                                C.sub.24 H.sub.25 ClN.sub.2 O.sub.4               10    C(CH.sub.3).sub.3                                                                        86-88  Calc:                                                                             65.37                                                                             5.72                                                                              6.35                                                              Found:                                                                            65.39                                                                             5.72                                                                              6.28                                                                  C.sub.27 H.sub.20 CF.sub.3 N.sub.2 O.sub.4        11                                                                                   ##STR43## 71-75  Calc: Found:                                                                      61.31 61.32                                                                       3.81 3.82                                                                         5.30 5.61                                                              C.sub.23 H.sub.23 ClN.sub.2 O.sub.4              12    CH(CH.sub.3).sub.2                                                                       45-49  Calc:                                                                             64.71                                                                             5.43                                                                              6.56                                                              Found:                                                                            64.51                                                                             5.37                                                                              6.63                                                                  C.sub.23 H.sub.23 ClN.sub.2 O.sub.4               13    C.sub.3 H.sub.7                                                                          yellow oil                                                                           Calc:                                                                             64.71                                                                             5.43                                                                              6.56                                                              Found:                                                                            64.55                                                                             5.46                                                                              6.76                                                                  C.sub.27 H.sub.20 ClF.sub.3 N.sub.2 O.sub.5       14                                                                                   ##STR44## 80-84  Calc: Found:                                                                      59.51 59.10                                                                       3.70 3.68                                                                         5.14 5.29                                                             C.sub.27 H.sub.23 ClN.sub.2 O.sub.4               15                                                                                   ##STR45## 70-74  Calc: Found:                                                                      68.28 68.25                                                                       4.88 4.88                                                                         5.90 5.95                                                             C.sub.28 H.sub.25 ClN.sub.2 O.sub.4               16                                                                                   ##STR46## 87-89  Calc: Found:                                                                      68.78 68.59                                                                       5.15 5.20                                                                         5.73 5.92                                                             C.sub.26 H.sub.20 ClN.sub.3 O.sub.6               17                                                                                   ##STR47## 99-103 Calc: Found:                                                                      61.73 62.13                                                                       3.98 4.11                                                                         8.31 8.28                                 __________________________________________________________________________

EXAMPLE 11 E isomer of4-(4-((6-chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol,4-chlorobenzoate ##STR48##

A nitrogen flushed solution of 1.78 g (5 mmol) of the pentenol obtainedin Example 3 above, 0.61 g (6 mmol) of triethylamine and 40 ml ofmethylene chloride was cooled in an ice bath. A solution of 1.05 g (6mmol) of 4-chlorobenzoyl chloride in 2 ml of methylene chloride wasslowly added, and the resulting solution allowed to stir at ambienttemperature overnight. The mixture was then poured into water, and theorganic layer separated and washed with saturated aqueous NaHCO₃ andsaturated aqueous NaCl, dried over MgSO₄ and evaporated to leave an oil.The oil was purified by preparative scale HPLC, eluting with 85:15hexane:ethyl acetate. After removal of the solvent, an oil was obtainedwhich, after trituration with hexane, solidified. The solid wasfiltered, washed with hexane and dried to give 1.91 g (77%) of thedesired ester melting at 96°-99° C. (Compound 18).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.26 H.sub.20 Cl.sub.2 N.sub.2 O.sub.4 :                                      63.04    4.07   5.66                                       Found:             62.41    3.99   5.71                                       ______________________________________                                    

By following the procedures of Examples 7 and 8 employing theappropriate starting pentenols and acid chloride, the followingcompounds in Table 4 are prepared.

                                      TABLE 4                                     __________________________________________________________________________     ##STR49##                                                                                             Molecular Formula and                                Compound     M.P. °C. or                                                                        Elemental Analysis                                   No.   R.sup.2                                                                              RI at (n.sub.D.sup.25)                                                                    % C % H % N                                          __________________________________________________________________________                             C.sub.26 H.sub.20 Cl.sub.2 N.sub.2 O.sub.4           19                                                                                   ##STR50##                                                                           63-65  Calc: Found:                                                                       63.04 62.53                                                                       4.07 4.07                                                                         5.66 5.64                                                             C.sub.26 H.sub.20 Cl.sub.2 N.sub.2 O.sub.4           20                                                                                   ##STR51##                                                                           thick gum                                                                            Calc: Found:                                                                       63.04 62.12                                                                       4.07 3.90                                                                         5.66 5.52                                                             C.sub.26 H.sub.19 Cl.sub.3 N.sub.2 O.sub.4           21                                                                                   ##STR52##                                                                           107-110                                                                              Calc: Found:                                                                       58.94 58.83                                                                       3.61 3.53                                                                         5.29 5.11                                    __________________________________________________________________________

EXAMPLE 12 4-(Aminocarbonyl)benzoic acid,4-(4-((6-chloro-2-quin-oxalinyl)oxy)phenoxy)-2-pentenyl ester ##STR53##

A mixture of 1.5 g (4.2 mmol) of the pentenol obtained in Example 3above, 1.04 g (6.3 mmol) of 4-(aminocarbonyl)benzoic acid, 1.30 g (6.3mmol) of dicyclohexylcarbodiimide (DCC), 0.05 g of4-(dimethylamino)pyridine and 20 ml of DMF was stirred at roomtemperature overnight. An additional 0.3 g of DCC and 0.25 g of4-(aminocarbonyl)benzoic acid are added and the mixture was stirred anadditional 20 hours. The mixture was then poured into ether, water addedand filtered. The filtrates were separated, and the organic layer washedwith saturated aqueous NaHC03 and water, dried over MgSO₄ and evaporatedto dryness. The residue was purified by preparative scale HPLC, elutingwith a 3:2 hexane:acetone, mixture to give 0.55 g of the desired productas a tan, glassy solid, m.p. 144°-148° C. (Compound 22).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.27 H.sub.22 ClN.sub.3 O.sub.5 :                                             64.35    4.40   8.34                                       Found:             63.97    4.70   8.06                                       ______________________________________                                    

EXAMPLE 13 4-(Acetylamino)benzoic acid,4-(4-((6-chloro-2-quinoxa-linyl)oxy)phenoxy)-2-pentenyl ester ##STR54##

A mixture of 1.5 g (4.2 mmol) of the pentenol obtained in Example 3above, 0.82 g (4.6 mmol) of 4-(acetylamino)benzoic acid, 0.95 g (4.6mmol) of dicyclohexylcarbodiimide and 0.05 g of4-(dimethylamino)pyridine in 20 ml of dimethylformamide was stirred atroom temperature for 72 hours. The mixture was diluted with ether andwater and filtered. The filtrates were separated, and the organic layerwashed with saturated aqueous NaHCO₃ and water, dried over MgSO₄ andevaporated to dryness. The residue was purified by preparative scaleHPLC, eluting with a 65:35 hexane:acetone mixture to give 0.6 g of thedesired product as a pale yellow, glassy solid, m.p. 62°-68° C.(Compound 23).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.28 H.sub.24 ClN.sub.3 O.sub.5 :                                             64.93    4.67   8.11                                       Found:             64.48    5.01   8.27                                       ______________________________________                                    

EXAMPLE 14 4-(4-((6-Chloro-2-quinoxalinyl)oxy)phenoxy)-2-penten-1-ol,methylcarbamate ##STR55##

To a solution of 1.78 g (5 mmol) of the pentenol obtained in Example 3above, and 50 ml of methylene chloride was added 3 drops oftriethylamine and 0.86 g (15 mmol) of methylisocyanate. The solution wasstirred at room temperature for 8 days. The solvent was separated andthe residue was recrystallized twice from methylcyclohexane to give 1.68g (81%) of the desired carbamate product as colorless crystals. Theproduct melted at 114°-115° C. (compound 24).

    ______________________________________                                        Elemental Analysis:                                                                            % C    % H    % N                                            ______________________________________                                        Calculated for C.sub.21 H.sub.20 ClN.sub.3 O.sub.4 :                                             60.97    4.87   10.15                                      Found:             60.69    4.81   10.43                                      ______________________________________                                    

The preparation of the optical isomer forms of the active compoundsfollow conventional procedures employed to prepare related compounds.Such procedures include those taught in U.S. Patent Applications No.4,532,328; European Patent Applications 2,800, 3,890 and 6,608; GermanOLS No. 2,949,728 and U.K. Patent Application No. GB 2,042,503A. Theteachings of these applications are incorporated herein by referencethereto.

The alkenol compounds of the present invention have been found to besuitable for use in methods for the pre- and postemergent control ofgrassy weeds. Such weeds involved, for example, foxtail, barnyard grass,wild oats, Johnson grass and crabgrass. In addition, these compounds canbe employed to control these grassy weeds in the presence of variousbroadleaf crop plants including sugar beets, soybeans, cotton, rape andthe like.

The derivative compounds prepared from the alkenol intermediates of thepresent invention have been found to be suitable for use in methods forthe selective postemergent control of many annual and perennial grassyweeds in the presence of corn plants.

It is to be noted that not all compounds will have the same effect onall weed plants. Some compounds will be more active in the control ofone weed specie than another.

For the above herbicidal uses, unmodified active ingredients of theactive compounds can be employed. However, the present invention alsoembraces the use of the active compounds in admixture with inertmaterials, known in the art as agricultural adjuvants and/or carriers,in solid or liquid form. Thus, for example, an active ingredient can bedispersed on a finely-divided solid and employed therein as a dust orgranule. Also, the active ingredients, as liquid concentrates or solidcompositions comprising one or more of the active ingredients can bedispersed in water, typically with aid of a wetting agent, and theresulting aqueous dispersion employed as a spray. In other procedures,the active ingredients can be employed as a constituent of organicliquid compositions, oil-in-water and water-in-oil emulsions or waterdispersions, with or without the addition of wetting, dispersing, oremulsifying agents. Suitable adjuvants of the foregoing type are wellknown to those skilled in the art.

The herbicidally effective concentration of the active ingredients insolid or liquid compositions generally is from about 0.0003 to about 95percent by weight or more. Concentrations from about 0.05 to about 50percent by weight are often employed. In compositions to be employed asconcentrates, the active ingredient can be present in a concentrationfrom about 5 to about 98 weight percent. The active ingredientcompositions can also contain other compatible additaments, for example,phytotoxicants, plant growth regulants and other biologically activecompounds used in agriculture.

In further embodiments, the compounds of the present invention orcompositions containing the same, can be advantageously employed incombination with one or more additional pesticidal compounds. Suchadditional pesticidal compounds may be insecticides, nematocides,miticides, arthropodicides, herbicides, fungicides or bactericides thatare compatible with the compounds of the present invention in the mediumselected for application and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the pesticidalcompound is employed as a supplemental toxicant for the same or for adifferent pesticidal use or as an additament. The compounds incombination can generally be present in a ratio of from 1 to 100 partsof the compound of the present invention with from 100 to 1 part of theadditional compound(s).

The derivative compounds taught to be prepared from the alkenols of thepresent invention have been found to possess desirable postemergentactivity against grassy weeds such as foxtail, barnyard grass, wildoats, Johnson grass and crabgrass while showing high selectivity to cornplants. These compounds are also uniquely effective in controllingperennial grassy weeds such as Johnson grass, quackgrass, and bermudagrass.

The exact amount of the active material to be applied is dependent notonly on the specific active ingredient being applied, but also on theparticular action desired, the weed plant species to be controlled andthe stage of growth thereof as well as the part of the plant to becontacted with the toxic active ingredient. Thus, all of the activeingredients of the present invention and compositions containing thesame may not be equally effective at similar concentrations or againstthe same weed plant species.

In the above taught pre- and postemergent operations, a dosage of about0.01 to about 20 lbs/acre (0.056-22.4 kg/hectare) is generallyapplicable, although not all compounds are equally effective and someweeds are more difficult to control. Thus, a dosage rate in the range ofabout 0.05 to about 1.0 lb/acre (0.01-1.12 kg/hectare) is preferred incontrol of annual grassy weeds, while about 0.05 to about 5 lbs/acre(0.056-5.6 kg/hectare) is a preferred dosage range for the control ofperennial grassy weeds.

The following examples illustrate the effects of the compounds of thisinvention.

EXAMPLE 15

Representative compositions of the present invention were evaluated todetermine their effectiveness in preemergent operations.

Aqueous dispersions were prepared by admixing predetermined amounts ofone of the hereinafter set forth compounds, dissolved in a predeterminedamount of an inert solvent with a predetermined quantity of water andsurfactant to dispersions of one of compound B or C as the soletoxicant.

These compositions were drenched soil onto the in plots immediatelyafter they were seeded with predetermined plant seeds. Other plotssimilarly seeded with the same plant species were drenched with likecompositions, containing no toxicant, to serve as controls. The plotswere treated at a treating rate equivalent to 1 and 0.5 pound per acre.Thereafter, the plots were maintained under conditions conducive to goodplant growth. Two weeks after treatment, the plots were examined todetermine the amount of plant growth. The results of the examinationsare set forth below in Table 5.

                                      TABLE 5                                     __________________________________________________________________________          Treating Rate                                                                        Percent Kill and Control of the Following Plant                               Species.sup.(a)                                                  Compound                                                                            In Pounds                                                                            at Indicated Treating Rate                                       Number                                                                              Per Acre                                                                             CT SOY                                                                              SB CN RC SG WH BG CG JG WO YFT                             __________________________________________________________________________    B     0.5    0  0  0  0  10 100                                                                              10 60 100                                                                              100                                                                              50 95                                    1.0    0  0  0  100                                                                              20 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              50 90                              C     0.5    0  0  0  100                                                                              70 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80 100                                   1.0    0  0  0  100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                             __________________________________________________________________________     .sup.(a) CT = cotton; SOY = soybean, SB = sugar beet; CN = corn; RC =         rice; SG = sorghum; WH = wheat; BG = barnyard grass; CG = crabgrass; JG =     Johnson grass; WO = wild oats and YFT = yellow foxtail.                  

EXAMPLE 16

Representative compositions of the present invention were evaluated todetermine their effectiveness in postemergent operations.

Aqueous dispersions were prepared by admixing predetermined amounts ofone of the hereinafter set forth compounds, dissolved in a predeterminedamount of an inert solvent with a predetermined quantity of water, and apredetermined amount of a surfactant to give aqueous dispersions ofcompounds B, C, D, E or F as the sole toxicant.

Predetermined plant seeds were planted in beds of good agricultural soiland grown in a greenhouse. After the plants had emerged and had grown toa height of about 4 inches, the plants were sprayed to runoff with oneof the above-prepared compositions at a predetermined treating rate (inparts of the active compound per million parts of the ultimatecomposition (PPM)). Other beds of the plants were sprayed with awater-surfactant mixture, containing no active compound, to serve ascontrols. After treatment, the beds were maintained for two weeks undergreenhouse conditions conducive for good plant growth. At the end ofthis period, the beds were examined to determine the amount of kill andcontrol. The specific plant species, test compounds and the percentpostemergent control are set forth below in Table 6.

                                      TABLE 6                                     __________________________________________________________________________          Treating Rate                                                                        Percent Kill and Control of the Following Plant                               Species.sup.(a)                                                  Compound                                                                            In Parts                                                                             at Indicated Treating Rate                                       Number                                                                              Per Million                                                                          CT SOY                                                                              SB CN RC SG WH BG CG JG WO FT                              __________________________________________________________________________    B     500    0  0  0  40 0  40 10 100                                                                              100                                                                              99 0  0                                     250    0  0  0  15 0  15 0  100                                                                              95 100                                                                              0  0                                     125    0  0  0  0  0  10 0  100                                                                              100                                                                              100                                                                              0  0                               C     250    0  0  0  100                                                                              90 90 100                                                                              100                                                                              100                                                                              100                                                                              70 100                                   125    0  0  0  40 85 100                                                                              20 100                                                                              90 100                                                                              70 100                                   62.5   0  0  0  20 80 100                                                                              20 100                                                                              95 100                                                                              20 100                             D     500    0  0  0  100                                                                              98 90 100                                                                              100                                                                              100                                                                              100                                                                              98 100                                   250    0  0  0  100                                                                              50 0  40 100                                                                              100                                                                              0  30 100                                   125    0  0  0  50 0  0  40 98 100                                                                              0  20 100                             E     500    0  0  100                                                                              100                                                                              100                                                                              0  0  100                                                                              NT 100                                                                              30 100                                   250    0  0  100                                                                              100                                                                              98 0  0  100                                                                              NT 100                                                                              30 100                             F     500    0  20 0  100                                                                              100                                                                              0  90 100                                                                              NT 100                                                                              98 100                                   250    0  0  0  100                                                                              100                                                                              0  90 100                                                                              100                                                                              90 90 100                             __________________________________________________________________________     .sup.(a) CT = cotton; SOY = soybean, SB = sugar beet; CN = corn; RC =         rice; SG = sorghum; WH = wheat; BG = barnyard grass; CG = crabgrass; JG =     Johnson grass; WO = wild oats and FT = foxtail. NT = not tested          

EXAMPLE 17

Representative compositions of the derivatives made from the alkenols ofthe present invention were evaluated to determine their effectiveness inpostemergent operations.

Aqueous dispersions were prepared by admixing predetermined amounts ofone of the hereinafter set forth compounds, dissolved in a predeterminedamount of an inert solvent with a predetermined quantity of water and apredetermined amount of a surfactant to give aqueous dispersions of oneof compounds 1-19 as the sole toxicant.

Predetermined plant seeds were planted in beds of good agricultural soiland grown in a greenhouse. After the plants had emerged and had grown toa height of from 2-8 inches, the plants were sprayed to runoff with oneof the above-prepared compositions at a predetermined treating rate (inparts of the active compound per million parts of the ultimatecomposition (PPM)). Other beds of the plants were sprayed with awater-surfactant mixture, containing no active compound, to serve ascontrols. After treatment, the beds were maintained for two weeks undergreenhouse conditions conducive for good plant growth. At the end ofthis period, the beds were examined to determine the amount of kill andcontrol. The specific plant species, test compounds and the percentpostemergent control are set forth below in Table 7.

                  TABLE 7                                                         ______________________________________                                                      Percent Kill and Control                                        Treatment     of the Following Plant Species                                  Compound                                                                              Rate in          Crab-                                                                              Johnson                                                                              Giant Green                              No. Tested                                                                            PPM       Corn   grass                                                                              Grass  Foxtail                                                                             Foxtail                            ______________________________________                                        1       1000      0      NT   90     85    90                                         500       0      NT   75     85    80                                 2       500       0      100  NT     100   100                                        250       0      100  NT     100   100                                3       250       0      NT   100    100   100                                        125       0      NT   100    100   100                                4       500       0      80   NT     98    98                                         250       0      80   NT     100   98                                 5       500       0      100  NT     100   100                                        250       0      100  NT     100   100                                6       500       0      98   NT     100   100                                        250       0      70   NT     98    100                                7       500       0      95   NT     100   98                                         250       0      90   NT     100   98                                 8       500       0      100  NT     100   100                                        250       0      100  NT     100   100                                9       500       10     NT   100    100   100                                        250       0      NT   100    100   100                                10      500       20     NT   100    100   100                                        250       0      NT   100    100   100                                11      62        10     NT   100    100   100                                        31        0      NT   80     90    20                                 12      125       20     NT   100    100   100                                        62        0      NT   100    100   100                                13      500       10     NT   100    100   100                                        250       0      NT   100    100   100                                14      250       20     NT   100    100   100                                        125       0      NT   100    90    50                                 15      500       20     NT   100    100   100                                        250       0      NT   100    100   100                                16      250       20     NT   100    100   100                                        125       0      NT   100    90    95                                 17      250       0      NT   NT     94    NT                                         125       0      NT   NT     92    NT                                 18      250       5      NT   NT     90    NT                                         125       5      NT   NT     90    NT                                 19      250       5      NT   NT     98    NT                                         125       0      NT   NT     98    NT                                 ______________________________________                                    

What is claimed is:
 1. A compound or an optical isomer thereofcorresponding to the formula ##STR56## wherein Y and Y¹ eachindependently represent --H or --F;P represents methyl or ethyl; Trepresents --CH₂ --CH₂ --_(a) CH═CH--_(b) and the cis (Z) or trans (E)stereoisomers thereof or --CH₂ --CH₂ --_(a) C.tbd.C; A represents.tbd.CH; a represents the integer 0, 1 or 2; b represents the integer 1or 2; and X represents --Br, --Cl, --F or --CF₃.
 2. A compound asdefined in claim 1 which is in the R enantiomeric isomer form.
 3. Acompound as defined in claim 1 which is in the E stereoisomer form.
 4. Acompound as defined in claim 1 wherein X is --Br, --Cl or --F, a is 0, bis 1 and P is methyl.
 5. A compound as defined in claim 4 wherein X is--Cl.
 6. The compound as defined in claim 5 which is4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol.
 7. The compoundas defined in claim 6 which is in the E stereoisomer form.
 8. A compoundas defined in claim 4 wherein X is --F.
 9. The compound as defined inclaim 8 which is4-(4-((6-fluoro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol.
 10. Acomposition which comprises an agriculturally acceptable inert adjuvantin intimate admixture with a herbicidally effective amount of a compoundor an optical isomer thereof, as the active material, which correspondsto the formula ##STR57## wherein Y and Y¹ each independently represent--H or --F;P represents methyl or ethyl; T represents --CH₂ --CH₂)_(a)(CH═CH--_(b) and the cis (Z) or trans (E) stereoisomers thereof or --CH₂--CH₂ --_(a) (C.tbd.C--; A represents .tbd.CH; a represents the integer0.1 or 2; b represents the integer 1 or 2; and X represents --Br, --Cl,--F or --CF₃.
 11. A composition as defined in claim 10 wherein thecompound is in the R enantiomeric isomer form.
 12. A composition asdefined in claim 10 wherein the compound is in the E stereoisomer form.13. A composition as defined in claim 10 wherein X is --Br, --Cl or --F,a is 0, b is 1 and P is methyl.
 14. A composition as defined in claim 13wherein X is --Cl.
 15. The composition as defined in claim 14 whereinthe compound is4-(4-((6-chloro-2-quinolinyl)-oxy)phenoxy)-2-penten-1-ol.
 16. Thecomposition as defined in claim 15 wherein the compound is in the Estereoisomer form.
 17. A composition as defined in claim 13 wherein X is--F.
 18. The composition as defined in claim 17 wherein the compound is4-(4-((6-fluoro-2-quinolinyl)-oxy)phenoxy)-2-penten-1-ol.
 19. A methodfor the postemergent kill and control of grassy weeds which comprisesapplying to said weeds a herbicidally effective amount of a compositioncomprising an agriculturally acceptable inert adjuvant in intimateadmixture with, as the active material, a compound or an optical isomerthereof, as the active material, which corresponds to the formula##STR58## wherein Y and Y¹ each independently represent --H or --F;Prepresents methyl or ethyl; T represents --CH₂ --CH₂)_(a) CH═CH--_(b)and the cis (Z) or trans (E) stereoisomers thereof or --CH₂ --CH₂ --_(a)C.tbd.CH--; A represents .tbd.CH; a represents the integer 0, 1 or 2; brepresents the integer 1 or 2; and X represents --Br, --Cl, --F or--CF₃.
 20. A method as defined in claim 19 wherein the compound is inthe R enantiomeric isomer form.
 21. A method as defined in claim 19wherein the compound is in the E stereoisomer form.
 22. A method asdefined in claim 19 wherein X is --Br, --Cl or --F, a is 0, b is 1 and Pis methyl.
 23. A method as defined in claim 22 wherein X is --Cl. 24.The method as defined in claim 23 wherein the compound is4-(4-((6-chloro-2-quinolinyl)oxy)phenoxy)-2-penten-1-ol.
 25. The methodas defined in claim 24 wherein the compound is in the E isomer form. 26.A method as defined in claim 22 wherein X is --F.
 27. The method asdefined in claim 26 wherein the compound is4-(4-((6-fluoro-2-quinolinyl)oxy)phenoxy-2-penten-1-ol.